skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors

Abstract

Arranging molecules into highly symmetric, topological crystal structures has been recognized as the best approach to functionalize electronic properties in molecular crystals, where the constituent molecules have been assumed to be rigid in shape. Here, in striking contrast, we demonstrate that the molecules in a monolayer organic crystal can undergo a significant deformation in proximity to the substrate, which is reflected by an asymmetry in the electron density profile. X-ray reflectivity and X-ray absorption spectroscopies in conjunction with density-functional theory calculations reveal that the highly planarized π-core are deformed into a bent shape, while the bulk lattice parameters are maintained. The molecular shape change is found to be perfectly suppressed in a bilayer single crystal, which leads to a 40% increase in mobility in the bilayer crystal. Our finding of a unique, sub-molecular scale shape change in monolayer single crystals can offer possibilities for functionalizing electrical properties via nano-scale physisorption.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4];  [5]; ORCiD logo [5]; ORCiD logo [5];  [6];  [6];  [1];  [7];  [1];  [1]
  1. Univ. of Tokyo (Japan). Dept. of Advanced Material Science; National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
  2. Osaka Univ. (Japan); Tohoku Univ., Sendai (Japan). Dept. of Physics
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. Hiroshima Univ. (Japan). Dept. of Chemistry
  5. Univ. of Tsukuba (Japan)
  6. Univ. of Tokyo (Japan). Dept. of Advanced Material Science
  7. Tohoku Univ., Sendai (Japan). Dept. of Physics
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605375
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Communications Physics
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2399-3650
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yamamura, Akifumi, Fujii, Hiromasa, Ogasawara, Hirohito, Nordlund, Dennis, Takahashi, Osamu, Kishi, Yuutaro, Ishii, Hiroyuki, Kobayashi, Nobuhiko, Niitsu, Naoyuki, Blülle, Balthasar, Okamoto, Toshihiro, Wakabayashi, Yusuke, Watanabe, Shun, and Takeya, Jun. Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors. United States: N. p., 2020. Web. doi:10.1038/s42005-020-0285-7.
Yamamura, Akifumi, Fujii, Hiromasa, Ogasawara, Hirohito, Nordlund, Dennis, Takahashi, Osamu, Kishi, Yuutaro, Ishii, Hiroyuki, Kobayashi, Nobuhiko, Niitsu, Naoyuki, Blülle, Balthasar, Okamoto, Toshihiro, Wakabayashi, Yusuke, Watanabe, Shun, & Takeya, Jun. Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors. United States. doi:https://doi.org/10.1038/s42005-020-0285-7
Yamamura, Akifumi, Fujii, Hiromasa, Ogasawara, Hirohito, Nordlund, Dennis, Takahashi, Osamu, Kishi, Yuutaro, Ishii, Hiroyuki, Kobayashi, Nobuhiko, Niitsu, Naoyuki, Blülle, Balthasar, Okamoto, Toshihiro, Wakabayashi, Yusuke, Watanabe, Shun, and Takeya, Jun. Thu . "Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors". United States. doi:https://doi.org/10.1038/s42005-020-0285-7. https://www.osti.gov/servlets/purl/1605375.
@article{osti_1605375,
title = {Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors},
author = {Yamamura, Akifumi and Fujii, Hiromasa and Ogasawara, Hirohito and Nordlund, Dennis and Takahashi, Osamu and Kishi, Yuutaro and Ishii, Hiroyuki and Kobayashi, Nobuhiko and Niitsu, Naoyuki and Blülle, Balthasar and Okamoto, Toshihiro and Wakabayashi, Yusuke and Watanabe, Shun and Takeya, Jun},
abstractNote = {Arranging molecules into highly symmetric, topological crystal structures has been recognized as the best approach to functionalize electronic properties in molecular crystals, where the constituent molecules have been assumed to be rigid in shape. Here, in striking contrast, we demonstrate that the molecules in a monolayer organic crystal can undergo a significant deformation in proximity to the substrate, which is reflected by an asymmetry in the electron density profile. X-ray reflectivity and X-ray absorption spectroscopies in conjunction with density-functional theory calculations reveal that the highly planarized π-core are deformed into a bent shape, while the bulk lattice parameters are maintained. The molecular shape change is found to be perfectly suppressed in a bilayer single crystal, which leads to a 40% increase in mobility in the bilayer crystal. Our finding of a unique, sub-molecular scale shape change in monolayer single crystals can offer possibilities for functionalizing electrical properties via nano-scale physisorption.},
doi = {10.1038/s42005-020-0285-7},
journal = {Communications Physics},
number = 1,
volume = 3,
place = {United States},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Sub-Å Resolution Electron Density Analysis of the Surface of Organic Rubrene Crystals
journal, February 2010


Inch-Size Solution-Processed Single-Crystalline Films of High-Mobility Organic Semiconductors
journal, July 2013

  • Soeda, Junshi; Uemura, Takafumi; Okamoto, Toshihiro
  • Applied Physics Express, Vol. 6, Issue 7
  • DOI: 10.7567/APEX.6.076503

A sensitivity-enhanced field-effect chiral sensor
journal, April 2008

  • Torsi, Luisa; Farinola, Gianluca M.; Marinelli, Francesco
  • Nature Materials, Vol. 7, Issue 5
  • DOI: 10.1038/nmat2167

Semiconductive Single Molecular Bilayers Realized Using Geometrical Frustration
journal, April 2018

  • Arai, Shunto; Inoue, Satoru; Hamai, Takamasa
  • Advanced Materials, Vol. 30, Issue 23
  • DOI: 10.1002/adma.201707256

Direct observation of the rotation of F1-ATPase
journal, March 1997

  • Noji, Hiroyuki; Yasuda, Ryohei; Yoshida, Masasuke
  • Nature, Vol. 386, Issue 6622
  • DOI: 10.1038/386299a0

Chiral switching by spontaneous conformational change in adsorbed organic molecules
journal, January 2006

  • Weigelt, Sigrid; Busse, Carsten; Petersen, Lars
  • Nature Materials, Vol. 5, Issue 2
  • DOI: 10.1038/nmat1558

Solution-Processable, Low-Voltage, and High-Performance Monolayer Field-Effect Transistors with Aqueous Stability and High Sensitivity
journal, February 2015

  • Chen, Hongliang; Dong, Shaohua; Bai, Meilin
  • Advanced Materials, Vol. 27, Issue 12
  • DOI: 10.1002/adma.201405378

Atomic-Level Characterization of the Structural Dynamics of Proteins
journal, October 2010


High-Performance Solution-Processable N-Shaped Organic Semiconducting Materials with Stabilized Crystal Phase
journal, May 2014

  • Mitsui, Chikahiko; Okamoto, Toshihiro; Yamagishi, Masakazu
  • Advanced Materials, Vol. 26, Issue 26
  • DOI: 10.1002/adma.201400289

High-performance, semiconducting membrane composed of ultrathin, single-crystal organic semiconductors
journal, December 2019

  • Makita, Tatsuyuki; Kumagai, Shohei; Kumamoto, Akihito
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 1
  • DOI: 10.1073/pnas.1909932116

Tracking the Chiral Recognition of Adsorbed Dipeptides at the Single-Molecule Level
journal, June 2007

  • Lingenfelder, Magalí; Tomba, Giulia; Costantini, Giovanni
  • Angewandte Chemie, Vol. 119, Issue 24
  • DOI: 10.1002/ange.200700194

Circularly polarized light detection by a chiral organic semiconductor transistor
journal, July 2013

  • Yang, Ying; da Costa, Rosenildo Correa; Fuchter, Matthew J.
  • Nature Photonics, Vol. 7, Issue 8
  • DOI: 10.1038/nphoton.2013.176

Dependence of single-molecule junction conductance on molecular conformation
journal, August 2006

  • Venkataraman, Latha; Klare, Jennifer E.; Nuckolls, Colin
  • Nature, Vol. 442, Issue 7105
  • DOI: 10.1038/nature05037

Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å
journal, April 2011

  • Umena, Yasufumi; Kawakami, Keisuke; Shen, Jian-Ren
  • Nature, Vol. 473, Issue 7345
  • DOI: 10.1038/nature09913

Additive, nanoscale patterning of metal films with a stamp and a surface chemistry mediated transfer process: Applications in plastic electronics
journal, July 2002

  • Loo, Yueh-Lin; Willett, Robert L.; Baldwin, Kirk W.
  • Applied Physics Letters, Vol. 81, Issue 3, p. 562-564
  • DOI: 10.1063/1.1493226

Ultrahigh mobility and efficient charge injection in monolayer organic thin-film transistors on boron nitride
journal, September 2017


Diffraction Pattern and Structure of Noncrystalline BeF 2 and SiO 2 at 25°C
journal, March 1972

  • Narten, A. H.
  • The Journal of Chemical Physics, Vol. 56, Issue 5
  • DOI: 10.1063/1.1677473

Contact resistance in organic transistors that use source and drain electrodes formed by soft contact lamination
journal, May 2003

  • Zaumseil, Jana; Baldwin, Kirk W.; Rogers, John A.
  • Journal of Applied Physics, Vol. 93, Issue 10
  • DOI: 10.1063/1.1568157

Biasing reaction pathways with mechanical force
journal, March 2007

  • Hickenboth, Charles R.; Moore, Jeffrey S.; White, Scott R.
  • Nature, Vol. 446, Issue 7134
  • DOI: 10.1038/nature05681

Early stages of collapsing pentacene crystal by Au
journal, October 2008

  • Ihm, Kyuwook; Chung, Sukmin; Kang, Tai-Hee
  • Applied Physics Letters, Vol. 93, Issue 14
  • DOI: 10.1063/1.2998539

Octahedral rotations in strained LaAlO 3 /SrTiO 3 (001) heterostructures
journal, February 2014

  • Fister, T. T.; Zhou, H.; Luo, Z.
  • APL Materials, Vol. 2, Issue 2
  • DOI: 10.1063/1.4865160

Quantitative Determination of Organic Semiconductor Microstructure from the Molecular to Device Scale
journal, June 2012

  • Rivnay, Jonathan; Mannsfeld, Stefan C. B.; Miller, Chad E.
  • Chemical Reviews, Vol. 112, Issue 10
  • DOI: 10.1021/cr3001109

Solution‐Processed 2D Molecular Crystals: Fabrication Techniques, Transistor Applications, and Physics
journal, October 2018

  • Qian, Jun; Jiang, Sai; Li, Songlin
  • Advanced Materials Technologies, Vol. 4, Issue 5
  • DOI: 10.1002/admt.201800182

Bottom-up growth of n-type monolayer molecular crystals on polymeric substrate for optoelectronic device applications
journal, July 2018


GenX : an extensible X-ray reflectivity refinement program utilizing differential evolution
journal, November 2007


2D Single-Crystalline Molecular Semiconductors with Precise Layer Definition Achieved by Floating-Coffee-Ring-Driven Assembly
journal, March 2016

  • Wang, Qijing; Qian, Jun; Li, Yun
  • Advanced Functional Materials, Vol. 26, Issue 19
  • DOI: 10.1002/adfm.201600304

Charge Transport in Organic Semiconductors
journal, April 2007

  • Coropceanu, Veaceslav; Cornil, Jérôme; da Silva Filho, Demetrio A.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr050140x

Coherent singlet fission activated by symmetry breaking
journal, May 2017

  • Miyata, Kiyoshi; Kurashige, Yuki; Watanabe, Kazuya
  • Nature Chemistry, Vol. 9, Issue 10
  • DOI: 10.1038/nchem.2784

Organosilicon dimer of BTBT as a perspective semiconductor material for toxic gas detection with monolayer organic field-effect transistors
journal, January 2018

  • Trul, Askold A.; Sizov, Alexey S.; Chekusova, Victoria P.
  • Journal of Materials Chemistry C, Vol. 6, Issue 36
  • DOI: 10.1039/C8TC02447B

Wafer-scale, layer-controlled organic single crystals for high-speed circuit operation
journal, February 2018

  • Yamamura, Akifumi; Watanabe, Shun; Uno, Mayumi
  • Science Advances, Vol. 4, Issue 2
  • DOI: 10.1126/sciadv.aao5758

Large surface relaxation in the organic semiconductor tetracene
journal, November 2014

  • Morisaki, Hazuki; Koretsune, Takashi; Hotta, Chisa
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6400

A map of high-mobility molecular semiconductors
journal, September 2017

  • Fratini, S.; Ciuchi, S.; Mayou, D.
  • Nature Materials, Vol. 16, Issue 10
  • DOI: 10.1038/nmat4970

Establishing Efficient Electrical Contact to the Weak Crystals of Triethylsilylethynyl Anthradithiophene
journal, October 2007

  • Dickey, Kimberly C.; Smith, Timothy J.; Stevenson, Keith J.
  • Chemistry of Materials, Vol. 19, Issue 22
  • DOI: 10.1021/cm071018c

Structure and Function of Photosystems i and ii
journal, June 2006


25th Anniversary Article: Key Points for High-Mobility Organic Field-Effect Transistors
journal, September 2013


Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit
journal, January 2016


Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors
journal, October 2014

  • He, Daowei; Zhang, Yuhan; Wu, Qisheng
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6162

Soft, conformable electrical contacts for organic semiconductors: High-resolution plastic circuits by lamination
journal, July 2002

  • Loo, Y.-L.; Someya, T.; Baldwin, K. W.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 16, p. 10252-10256
  • DOI: 10.1073/pnas.162128299

Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface
journal, July 2017

  • Shiotari, Akitoshi; Nakae, Takahiro; Iwata, Kota
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms16089

A general purpose sub-keV X-ray facility at the Stanford Synchrotron Radiation Laboratory
journal, May 1990

  • Tirsell, K. Glenn; Karpenko, Victor P.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 291, Issue 1-2
  • DOI: 10.1016/0168-9002(90)90113-K

Effects of metal penetration into organic semiconductors on the electrical properties of organic thin film transistors
journal, September 2006

  • Cho, Jeong Ho; Kim, Do Hwan; Jang, Yunseok
  • Applied Physics Letters, Vol. 89, Issue 13
  • DOI: 10.1063/1.2357155

Dynamic layer rearrangement during growth of layered oxide films by molecular beam epitaxy
journal, August 2014

  • Lee, J. H.; Luo, G.; Tung, I. C.
  • Nature Materials, Vol. 13, Issue 9
  • DOI: 10.1038/nmat4039

Mechanochemistry:  The Mechanical Activation of Covalent Bonds
journal, August 2005

  • Beyer, Martin K.; Clausen-Schaumann, Hauke
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr030697h

Tuning charge transport in solution-sheared organic semiconductors using lattice strain
journal, December 2011

  • Giri, Gaurav; Verploegen, Eric; Mannsfeld, Stefan C. B.
  • Nature, Vol. 480, Issue 7378, p. 504-508
  • DOI: 10.1038/nature10683

Occurrence of the potent mutagens 2- nitrobenzanthrone and 3-nitrobenzanthrone in fine airborne particles
journal, January 2019

  • Santos, Aldenor G.; da Rocha, Gisele O.; de Andrade, Jailson B.
  • Scientific Reports, Vol. 9, Issue 1
  • DOI: 10.1038/s41598-018-37186-2

One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films
journal, April 2014

  • Giri, Gaurav; Li, Ruipeng; Smilgies, Detlef-M
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4573

Solution-Processed Monolayer Organic Crystals for High-Performance Field-Effect Transistors and Ultrasensitive Gas Sensors
journal, May 2017

  • Peng, Boyu; Huang, Shuyun; Zhou, Zhiwen
  • Advanced Functional Materials, Vol. 27, Issue 29
  • DOI: 10.1002/adfm.201700999

A New Pentacene Polymorph Induced by Interaction with a Bi(0001) Substrate
journal, February 2018

  • Shirasawa, Tetsuroh; Yanagisawa, Susumu; Hatada, Shin-nosuke
  • The Journal of Physical Chemistry C, Vol. 122, Issue 11
  • DOI: 10.1021/acs.jpcc.8b00892

Mechanochemistry: The Mechanical Activation of Covalent Bonds
journal, October 2005